• Polymer(Korea)
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• v.33 no.5
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• pp.458-462
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• 2009

We have synthesized ABC linear triblock copolymers, i.e., polystyrene-b-poly(ethylene oxide)-b-polylactide, via sequential anionic and ring-opening polymerizations. In the first anionic polymerization step, styrene was polymerized in cyclohexane using sec-butyllithium as the initiator. Poly (styryl) lithium was hydroxylated by the addition of ethylene oxide, and the subsequent protonation with methanolic HCl. In the second anionic polymerization step, potassium naphthalenide was used to deprotonate the hydroxyl group of the PS to generate the macroinitiator of PS-$O^-K^+$. Polymerization of ethylene oxide was performed in THF and terminated with methanolic HCl. In the ring-opening polymerization step, the PS-b-PEO-$AlEt_2$ macroinitiator was prepared from an $AlEt_3$/pyridine system in THF, and the polymerization of lactide was performed at $90^{\circ}C$. The resulting block copolymers showed well-defined molecular weights and narrow molecular weight distributions as revealed by $^1H$- NMR spectroscopy and gel permeation chromatography (GPC).

• Composites Research
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• v.32 no.6
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• pp.375-381
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• 2019

Multiwalled carbon nanotubes (MWCNTs) are covalently functionalized with isocyanates by directly reacting commercial hydroxyl functionalized MWCNTs with excess 4,4'-methylenebis (phenyl isocyanate) (MDI) and hexamethylene diiosocyanate (HDI). HDI-modified MWCNTs results in a higher surface isocyanate density than MDI-modified MWCNTs. Anionic ring-opening polymerization of ε-caprolactam is conducted using a sodium caprolactam initiator in combination with a di-functional hexamethylene-1,6-dicarbamoylcaprolactam activator in the presence of isocyanate functionalized MWCNTs. This polymerization proceeds in a highly efficient manner at relatively low reaction temperature (150℃) and short reaction times (10 min). During the polymerization, the isocyanate functionalized MWCNTs act not only as reinforcing fillers but also as second activators. Nanocomposites with HDI modified MWCNTs exhibit higher reinforcement and faster isothermal crystallization than MDI modified MWCNTs. The results show that PA6 chains grow more effectively from HDI modified MWCNT surface than from MDI modified MWCNT surface, resulting in stronger interaction between PA6 and MWCNTs.

• Bulletin of the Korean Chemical Society
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• v.7 no.3
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• pp.210-213
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• 1986

1,1-Dicyano-2-ethoxycyclobutane (1a) was prepared by [2 + 2] cycloaddition reaction of vinylidene cyanide with ethyl vinyl ether. 1,1-Dicyano-2-phenylcyclobutane (1b) was prepared by the reactions involving the reduction of cinnamyl alcohol, chlorination, cyanomethylation, bromination, and ring-closure reaction. Compound 1a was ring-opening polymerized with NaCN or n-butyllithium to give a low molecular weight polymer. The compound 1b however, failed to polymerize by either anionic or radical catalysts.

• Polymer(Korea)
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• v.38 no.6
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• pp.714-719
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• 2014

Bio-based nylon 6-morpholinone random copolymers were prepared by the anionic ring opening polymerization of ${\varepsilon}$-caprolactam and morpholinone, both of which were prepared from lysine and glucose, respectively. From this work, a new biomass based nylon 6 with improved hydrophilicity was prepared. Optimizing the polymerization condition, copolymer with a viscosity-average molecular weight of 30000 g/mol was prepared, with a yield of 80%. It was possible to improve the hydrophilicity of nylon 6 by its copolymerization with morpholinone. The prepared nylon 6-morpholinone random copolymers were then characterized using several analytical methods such as DSC, TGA, XRD, viscosity measurement with U-shaped glass capillary viscometer and contact angle measurement.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.104-105
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• 2006

We succeeded the synthesis of new functional polymers by novel ring-opening addition reactions of bis(oxetane)s with diacyl chlorides, di(active ester)s, and di(carboxylic acid)s using quaternary onium salts as catalysts at appropriate conditions. Hyperbranched polyesters with many pendant hydroxy groups were also synthesized by the polyaddition of bis(oxetane)s with tricarboxylic acid, or by the self-polyadditions of $AB_2\;or\;A_2B$ type monomers containing oxetane group. The anionic ring-opening polymerization of (3-ethyl-3-hydroxymethyl)oxetane was examined using sodium tert-buthoxide to give hyperbranched poly(ether)s containing one oxetanyl group and many hydroxyl groups in the end of polymer chain.

• Polymer(Korea)
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• v.38 no.1
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• pp.9-15
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• 2014

Polyamide4 (PA4)-polyurethane (PU)-PA4 triblock copolymers were synthesized by isocynated (NCO)-terminated PU prepared from 4,4'-diphenyl methane diisocyante (MDI) and polytetramethylene glycol (PTMG) as an initiator and potassium pyrrolidonate (P-py) as a catalyst for anionic ring opening polymerization of 2-pyrrolidone. Subsequently copolymer was controlled to contain different or same molecular weight of PA4 hard block with same or different molecular weight of PU soft block in order to investigate the effects of those differences on various properties of triblock copolymers as a thermoplastic elastomer. As the results shown in typical properties of block copolymeric elastomers, the mechanical strength and melting point ($T_m$) of the copolymers increased with an increase in molecular weight of PA4 block while the elongation at break increased with an increase in that of PU block.

• Bulletin of the Korean Chemical Society
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• v.19 no.3
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• pp.328-332
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• 1998

Anionic ring-opening polymerization of 3,4-[(dimethylsilyl)isopropyl]benzo-1,1-dimethyl-1-silacyclopentene in the presence of n-butyllithium and HMPA in THF at - 78 ℃ afforded poly[3,4-(dimethylsilylisopropyl)benzo-1,1-dimethyl-1-silapentene]. The characteristic Si-H stretching frequency in the IR is observed at 2100 cm-1. The polycarbosilane has been modified by chloroplatinic acid catalyzed addition of styrene to the polycarbosilane SiH units. Molecular weights and thermal properties of the polymers were compared. The sol-gel polymerization of 3,4-[(dimethoxysilyl)isopropyl]benzo-1,1-dimethoxy-1-silacyclopentene in the presence of aqueous HCl or NaOH in THF resulted in a cross-linked polysiloxane. The xerogel has a low surface area of 13-14 m2/g and is stable up to about 400 ℃ with only 5% weight loss under a nitrogen atmosphere.

• Polymer(Korea)
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• v.38 no.1
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• pp.31-37
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• 2014

To prepare biomass based nylon 6,5 copolymers, ${\varepsilon}$-caprolactam and 2-piperidone, the monomers of nylon 6,5 copolymers, were synthesized respectively from lysine and 5-aminovaleric acid which were produced from glucose by the fermentation process. The copolymers were then polymerized by the anionic ring opening polymerization of them at $40^{\circ}C$, using potassium tert-butoxide as a catalyst and acetyl-2-caprolactam and carbon dioxide as initiators. The prepared copolymers were characterized with various analytical methods: their viscosity molecular weight ($M_{\eta}$) was as high as 30000 g/mol and polymerization yield was over 50%, and it was found that they were semi-crystalline polymers having melting point at $165^{\circ}C$ which was much lower than its thermal degradation point, $250^{\circ}C$. These polymers were expected to have good thermal processability and application fields.

• Polymer(Korea)
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• v.31 no.4
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• pp.322-328
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• 2007

Mono-dispersed polyamide 6(Nylon 6) micro-particles sized in $4{\sim}5\;{\mu}m$ diameter were prepared by dispersion polymerization of ${\varepsilon}-caprolactam$ in liquid paraffin as a dispersion medium. Potassium metal(K) as a catalyst was separately added twice over the anionic ring-opening polymerization of ${\varepsilon}-caprolactam$. The size, shape, and size-distribution of prepared particles were varied with the concentration of anti-coagulant as well as the amount of initiator and catalyst. As the initiator concentration was in the range of $0.97{\sim}1.17\;wt%$ in monomer, about 90.6% of yield was accomplished. In addition, the highest yield of well-spherically shaped micro-particles was achieved by adding about $1.3{\sim}1.4\;wt%$ of catalyst.

• Macromolecular Research
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• v.17 no.10
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• pp.770-775
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• 2009

$\omega$-Anhydride-functionalized poly(ethylene oxide) (PEO) obtained from chain-end functionalization and anionic ring-opening polymerization of ethylene oxide using n-butyllithium with potassium t-butoxide in the presence of dimethylsulfoxide (DMSO) was found to be an efficient material for the preparation of water-soluble, polymeric pro-drugs. The reaction of $\omega$-anhydride-functionalized PEO with sulfonamide or with vancomycin provided an efficient method to produce corresponding, water-soluble, PEO-conjugated sulfonamide or PEO-conjugated, vancomycin pro-drugs. These were used successfully to prepare water-dispersible, silver nanoparticles. In this study, the particle sizes were in the range of $5{\sim}40$ nm. The resulting products were characterized by $^1H$ NMR spectroscopy, transmission electron microscopy, electron and X-ray diffraction, size exclusion chromatography, and UV/Visible spectroscopy.